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US8759199B2 - Method of selectively growing semiconductor carbon nanotubes using light irradiation - Google Patents

Method of selectively growing semiconductor carbon nanotubes using light irradiation Download PDF

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Publication number
US8759199B2
US8759199B2 US12/879,087 US87908710A US8759199B2 US 8759199 B2 US8759199 B2 US 8759199B2 US 87908710 A US87908710 A US 87908710A US 8759199 B2 US8759199 B2 US 8759199B2
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Prior art keywords
carbon nanotubes
nanodots
substrate
semiconductor carbon
irradiating
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US12/879,087
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US20110111577A1 (en
Inventor
Won-mook CHOI
Jae-Young Choi
Jin Zhang
Guo HONG
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Samsung Electronics Co Ltd
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Samsung Electronics Co Ltd
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Assigned to SAMSUNG ELECTRONICS CO., LTD. reassignment SAMSUNG ELECTRONICS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHOI, JAE-YOUNG, CHOI, WON-MOOK, HONG, GUO, ZHANG, JIN
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/123—Ultraviolet light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/22—Electronic properties

Definitions

  • the present invention relates to a semiconductor carbon nanotubes and methods of selectively growing the semiconductor carbon nanotubes using light irradiation.
  • Carbon nanotubes have been intensively studied due to their one-dimensional structure, controllable conductivity, and unique mechanical strength.
  • the as grown semiconductor carbon nanotubes may be removed together with the metallic carbon nanotubes when removing the metallic carbon nanotubes, thereby decreasing yield. Furthermore, when the metallic carbon nanotubes are removed from a mixture including the semiconductor carbon nanotubes and the metallic carbon nanotubes, the removing process may cause an undesirable structural defect in the semiconductor carbon nanotubes.
  • a method of selectively growing a plurality of semiconductor carbon nanotubes using light irradiation when the plurality of carbon nanotubes are manufactured is disclosed.
  • a method of selectively growing the plurality of semiconductor carbon nanotubes using light irradiation includes disposing a plurality of nanodots, which include a catalyst material, on a substrate; growing a plurality of carbon nanotubes from the plurality of nanodots, and irradiating light onto the plurality of nanodots to selectively grow the plurality of semiconductor carbon nanotubes.
  • the substrate may be a sapphire substrate, and the plurality of carbon nanotubes may grow in a direction which is parallel to a crystallographic direction of the substrate.
  • the disposing of the plurality of nanodots may include disposing the plurality of nanodots in a row in a first direction, which is perpendicular to the crystallographic direction of the substrate.
  • the irradiating light onto the plurality of nanodots may include irradiating light on to the substrate through a slit which is elongated in the first direction.
  • the irradiating of light onto the plurality of nanodots may further include irradiating an ultraviolet ray having a wavelength of about 10 nanometers (nm) to about 1000 nm.
  • the irradiating of light onto the plurality of nanodots may further include irradiating an ultraviolet ray having a wavelength of about 10 nm to about 400 nm.
  • the irradiating light onto the plurality of nanodots may further include disposing the slit above an interface between the plurality of nanodots and the plurality of carbon nanotubes; and irradiating a light through the slit and onto the interface.
  • At least one of the growing of the plurality of carbon nanotubes or the selectively growing the plurality of semiconductor carbon nanotubes may include contacting the plurality of nanodots with a carbonaceous material, wherein the carbonaceous material is acetylene, ethylene, ethanol, methane, or a combination including at least one of the foregoing.
  • the apparatus includes a reaction chamber having a slit; a substrate disposed in the reaction chamber; and a plurality of nanodots disposed on the substrate in a region corresponding to the slit; wherein the slit is elongated in a direction perpendicular to a crystallographic direction of the substrate.
  • the apparatus may further include an ultraviolet light.
  • the ultraviolet light may be irradiated through the slit and onto the substrate.
  • the plurality of nanodots is disposed in a row.
  • the row is disposed in a direction perpendicular to a crystallographic direction of the substrate.
  • the row is disposed in a direction which is parallel to a direction in which the slit is elongated.
  • the row is disposed in a region corresponding to the slit.
  • FIGS. 1 through 4 are perspective views which illustrate an embodiment of a method of selectively growing semiconductor carbon nanotubes using light irradiation
  • FIG. 5 is a graph of intensity (arbitrary units, a.u.) versus Raman shift (inverse centimeters, cm ⁇ 1 ) showing a Raman spectrum of an embodiment of carbon nanotubes in a region A of FIG. 4 ;
  • FIG. 6 is a graph of intensity (arbitrary units, a.u.) versus Raman shift (inverse centimeters, cm ⁇ 1 ) showing a Raman spectrum of an embodiment of semiconductor carbon nanotubes in a region B of FIG. 4 ;
  • FIG. 7 is a graph of intensity (arbitrary units, a.u.) versus Raman shift (inverse centimeters, cm ⁇ 1 ) showing a Raman spectrum of an embodiment of a selectively grown semiconductor carbon nanotubes;
  • FIG. 8 is a graph of current (microamperes, ⁇ A) versus volts (volts, V) showing current-voltage (“IV”) characteristics of an embodiment of a field effect transistor using carbon nanotubes grown according to an embodiment as a channel of the field effect transistor.
  • first, second, third etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present invention.
  • spatially relative terms such as “beneath,” “below,” “lower,” “above,” “upper” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the exemplary term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
  • Embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
  • FIGS. 1 through 4 are perspective views which illustrate an embodiment of a method of selectively growing semiconductor carbon nanotubes using light irradiation.
  • a plurality of nanodots 110 which comprise a catalyst material, are disposed on a substrate 100 .
  • the substrate 100 may be a sapphire substrate, and the carbon nanotubes may be grown in a substantially horizontal direction along a crystallographic direction (such as an X direction as shown in FIG. 1 ) of the substrate 100 .
  • the horizontal direction may be a direction which is parallel to a plane of the substrate, such as the X direction indicated in FIG. 1 .
  • the plurality of nanodots 110 may comprise at least one of Ni, Co, Fe, or an alloy thereof, and may be disposed (e.g., formed) on the substrate 100 .
  • the plurality of nanodots 110 may have a diameter of about 10 nanometers (nm) to about 1000 nm, specifically about 50 nm to about 500 nm, more specifically about 100 nm to about 250 nm.
  • the plurality of nanodots 110 may be arranged in a Y direction a selected distance apart from each other. As shown in FIG. 1 , the plurality of nanodots 110 may be arranged linearly, but the present disclosure is not limited thereto.
  • a plurality of nanodots 110 may be disposed along a distance of less than or equal to about 5 millimeters (mm), specifically less than or equal to about 4 mm, more specifically less than or equal to about 1 mm.
  • the plurality of nanodots may be disposed along a distance of about 0.001 mm to about 5 mm, specifically about 0.01 to about 4 mm, more specifically about 0.1 mm to about 1 mm.
  • the plurality of nanodots 110 may be previously manufactured, but the present invention is not limited thereto.
  • the plurality of nanodots 110 may be formed by patterning a catalyst thin film, which comprises a catalyst material, after disposing (e.g., forming) the catalyst thin film on the substrate 100 .
  • the substrate 100 may be placed in a reaction chamber 122 of a chemical vapor deposition (“CVD”) apparatus.
  • CVD chemical vapor deposition
  • FIG. 2 shows only a portion of an upper part of the reaction chamber 122 .
  • a slit 120 is disposed (e.g., formed) in the upper part of the reaction chamber 122 .
  • the slit 120 may be disposed (e.g., formed) inside the reaction chamber 122 or on the reaction chamber 122 .
  • the plurality of nanodots 110 are arranged in a Y direction, and the slit 120 is elongated in the Y direction, as shown in FIG. 2 .
  • the slit 120 may be disposed (e.g., formed) to have a width D1 of approximately 10 mm, specifically about 8 mm, more specifically about 6 mm in the X direction.
  • the slit 120 may be separated by approximately a few mm, e.g., about 0.1 mm to about 10 mm, specifically about 0.5 m to about 8 mm, more specifically about 1 mm to about 5 mm, from the plurality of nanodots 110 in the X direction.
  • UV irradiation apparatus (not shown) may be disposed above the reaction chamber 122 .
  • a UV ray 140 irradiated from the UV irradiation apparatus may be irradiated through the slit 120 onto firstly grown carbon nanotubes 130 (refer to FIG. 3 ), which are grown on the substrate 100 .
  • the UV ray 140 may have a wavelength of about 10 nm to about 1000 nm, specifically about 100 nm to about 800 nm, more specifically about 10 nm to about 400 nm.
  • UV ray a light having a wavelength of about 10 nanometers to about 1000 nm, specifically about 100 nm to about 800 nm, more specifically about 10 nm to about 400 nm, may be used.
  • a carbon containing gas for example, acetylene, ethylene, ethanol, methane, or a combination comprising at least one of the foregoing, is supplied into the reaction chamber 122 .
  • the carbon containing gas is contacted with the substrate 100 , and the firstly grown carbon nanotubes 130 may linearly grow along a crystallographic direction (e.g., the X direction) of the substrate 100 from the plurality of nanodots 110 .
  • the X direction may be a [100], [101], or a [001] direction of the substrate, for example.
  • a carbon nanotube may linearly grow from each respective nanodot of plurality of nanodots.
  • the firstly grown carbon nanotubes 130 Prior to irradiating with a UV ray, the firstly grown carbon nanotubes 130 may have a length of about 0.01 mm to about 10 mm, specifically about 1 mm to about 8 mm, more specifically about 2 mm to about 6 mm, thus the carbon nanotube may have a length of a few mm.
  • the firstly grown carbon nanotubes 130 which are grown prior to irradiating with the UV ray, may include metallic carbon nanotubes and semiconductor carbon nanotubes.
  • each carbon nanotube of the firstly grown carbon nanotubes 130 may be a metallic carbon nanotube or a semiconductor carbon nanotube.
  • FIG. 5 is a Raman spectrum of the firstly grown carbon nanotubes 130 in a region A of FIG. 4
  • FIG. 6 is a Raman spectrum of the semiconductor carbon nanotubes 134 in a region B of FIG. 4 .
  • a laser beam having a wavelength of 514.5 nm is used to obtain the Raman spectrums of FIGS. 5 and 6 .
  • “S” indicates peaks of the semiconductor carbon nanotubes 134
  • “M” indicates peaks of the metallic carbon nanotubes 132 .
  • region A includes both the metallic carbon nanotubes, e.g. metallic carbon nanotubes 132 , and the semiconductor carbon nanotubes, e.g., the semiconductor carbon nanotubes 134 .
  • FIG. 7 is a graph of a Raman spectrum of an embodiment of selectively grown semiconductor carbon nanotubes. Referring to FIG. 7 , a well-developed peak is seen at a wave number of 1590 inverse centimeters (cm ⁇ 1 ), and a defect peak is effectively not present at a wave number of 1350 cm ⁇ 1 . This shows that a UV laser ray does not generate a defect in the structure of the grown semiconductor carbon nanotubes.
  • FIG. 8 is a graph showing current-voltage (“IV”) characteristics of a field effect transistor using carbon nanotubes grown according to an embodiment as a channel of the field effect transistor.
  • a bias voltage applied to the carbon nanotube field effect transistor was 100 millivolts (mV)
  • a channel length was 5.6 micrometers ( ⁇ m)
  • a thickness of a silicon oxide on a back gate comprising a silicon substrate was 800 nm.
  • the On/Off ratio of the field effect transistor which is a characteristic of a transistor, was 10 4 or greater.
  • the term On/Off ratio refers to a ratio of the source-drain current when a transistor is on to the source-drain current when the transistor is off.
  • the reason why the growing of the metallic carbon nanotubes 132 is repressed when an UV ray is irradiated thereto is that the UV ray makes a carbon source, such as methane (e.g., CH 4 ), include a free radical, and the free radical hinders the growing of the metallic carbon nanotube by selectively attacking the metallic carbon nanotube.
  • a carbon source such as methane (e.g., CH 4 )
  • methane e.g., CH 4
  • a process of removing metallic carbon nanotubes may be substantially reduced or effectively eliminated, and thus, a manufacturing yield of the semiconductor carbon nanotubes may be increased.

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  • Condensed Matter Physics & Semiconductors (AREA)
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US20110162957A1 (en) * 2009-11-25 2011-07-07 Massachusetts Institute Of Technology Systems and methods for enhancing growth of carbon-based nanostructures
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US9024310B2 (en) * 2011-01-12 2015-05-05 Tsinghua University Epitaxial structure
CN104609386B (zh) * 2013-11-05 2017-01-11 北京大学 单壁碳纳米管的定位生长方法
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